Organic Chemistry,

9th Edition
L. G. Wade, Jr.

Chapter 18
Lecture
Ketones and
Aldehydes

Chad Snyder, PhD

Grace College
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Classes of Carbonyl
Compounds

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 Structure of the Carbonyl Group

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Structure of the Carbonyl Group

(Continued)

• Carbon is sp2 hybridized.

• The C═O bond is shorter, stronger, and more polar
than the C═C bond in alkenes.
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 Resonance

• The first resonance is better because all atoms complete

the octet and there are no charges.
• The carbonyl carbon has a partial positive and will react as
an electrophile.

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Dipole Moments

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 Ketone Nomenclature

• Number the chain so that the carbonyl carbon

has the lowest number.
• Replace the alkane -e with -one.

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Cyclic Ketone Nomenclature

• For cyclic ketones, the carbonyl carbon is assigned the

number 1.
• When the compound has a carbonyl and a double
bond, the carbonyl takes precedence.
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 Aldehydes Nomenclature

• The aldehyde carbon is number 1.

• IUPAC: Replace -e with -al.
• If the aldehyde group is attached to a ring, the
suffix -carbaldehyde is used.
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Carbonyl as Substituent
• On a molecule with a higher-priority functional
group, a ketone is an oxo and an aldehyde is a
formyl group.
• Aldehydes have a higher priority than ketones.

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 Functional Group Priority

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Common Names for Ketones

• Named as alkyl attachments to —C═O
• Use Greek letters instead of numbers.

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 Common Names of Acids
and Aldehydes

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Historical Common Names

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 Boiling Points

• Ketones and aldehydes are more polar, so they

have a higher boiling point than comparable
alkanes or ethers.
• They cannot hydrogen-bond to each other, so their
boiling point is lower than the comparable alcohol.

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Solubility of Ketones
and Aldehydes
• Good solvent for alcohols
• Lone pair of electrons on oxygen of carbonyl can
accept a hydrogen bond from O—H or N—H.
• Acetone and acetaldehyde are miscible in water.

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Formaldehyde

• Gas at room temperature

• Formalin is a 40% aqueous solution.
• Trioxane is a cyclic trimer of formaldehyde.
• When trioxane is heated, it generates formaldehyde.
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 Infrared (IR) Spectroscopy

• Very strong C═O stretch around 1710 cm–1 for ketones and
1725 cm–1 for simple aldehydes
• Additional C—H stretches for aldehyde: Two absorptions at
2710 cm–1 and 2810 cm–1

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IR Spectra

• Conjugation lowers the carbonyl stretching

frequencies to about 1685 cm–1.
• Rings that have ring strain have higher C═O
frequencies.
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 Proton NMR Spectra

• Aldehyde protons normally absorb between

δ 9 and δ 10.
• Protons of the α carbon usually absorb
between δ 2.1 and δ 2.4 if there are no other
electron-withdrawing groups nearby.
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1H NMR Spectroscopy

• Protons closer to the carbonyl group are more deshielded.

• The α, β, and γ protons appear at values of δ that decrease
with increasing distance from the carbonyl group.

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 Carbon NMR Spectra of Ketones

• The spin-decoupled carbon NMR spectrum of 2-heptanone

shows the carbonyl carbon at 208 ppm and the α carbon at
30 ppm (methyl) and 44 ppm (methylene).
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Mass Spectrometry (MS)

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 MS for Butyraldehyde

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McLafferty Rearrangement

• The net result of this rearrangement is the breaking of the

α, β bond and the transfer of a proton from the γ carbon to
the oxygen.
• An alkene is formed as a product of this rearrangement
through the tautomerization of the enol.

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 Industrial Importance

• Acetone and methyl ethyl ketone are

common industrial solvents.
• Formaldehyde is used in polymers like
Bakelite and many other polymeric
products.
• Also used as flavorings and additives
for food

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 Grignards As a Source for
Ketones and Aldehydes

• A Grignard reagent can be used to make an

alcohol, and then the alcohol can be easily
oxidized.
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Oxidation of Primary
Alcohols to Aldehydes

• Pyridinium chlorochromate (PCC) is selectively

used to oxidize primary alcohols to aldehydes.
• The Swern oxidation could also be used.

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 Hydration of Alkynes

• The initial product of Markovnikov hydration is an enol,

which quickly tautomerizes to its keto form.
• Internal alkynes can be hydrated, but mixtures of ketones
often result.
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Synthesis of Ketones from

Carboxylic Acids

• Organolithiums will attack the lithium salts of

carboxylate anions to give dianions.
• Protonation of the dianion forms the hydrate of a
ketone, which quickly loses water to give the ketone.

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 Nucleophilic Addition

• A strong nucleophile attacks the carbonyl

carbon, forming an alkoxide ion that is then
protonated.
• Aldehydes are more reactive than ketones.
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Reaction with a
Grignard Reagent

• A strong nucleophile attacks the carbonyl carbon,

forming an alkoxide ion that is then protonated.

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 Reaction with a Hydride

• The hydride anion adds to the carbonyl carbon; the

alkoxide is protonated to form an alcohol.

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Electrophilic Strength

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 Hydration of Ketones and
Aldehydes

• In an aqueous solution, a ketone or an aldehyde is in

equilibrium with its hydrate, a geminal diol.
• With ketones, the equilibrium favors the unhydrated
keto form (carbonyl).
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Acid-Catalyzed Hydration
of Carbonyls

• Hydration occurs through the nucleophilic addition

mechanism, with water (in acid) or hydroxide (in base)
serving as the nucleophile.
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 Base-Catalyzed Hydration
of Carbonyls

• The hydroxide ion attacks the carbonyl group.

• Protonation of the intermediate gives the hydrate.

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Cyanohydrin Formation

• The mechanism is a base-catalyzed nucleophilic addition:

attack by cyanide ion on the carbonyl group, followed by
protonation of the intermediate.
• HCN is highly toxic.

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 Cyanohydrin Reactions

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Formation of Imines

• Ammonia or a primary amine reacts with a ketone or an

aldehyde to form an imine.
• Imines are nitrogen analogues of ketones and aldehydes
with a C═N bond in place of the carbonyl group.
• Optimum pH is around 4.5.

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 Mechanism of Imine Formation
Acid-catalyzed addition of the amine to the carbonyl
compound group

Acid-catalyzed dehydration

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Imine Reactions

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 Other Condensations
with Amines

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Formation of Acetals

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 Mechanism for
Hemiacetal Formation

• Must be acid-catalyzed
• Adding H+ to carbonyl makes it more reactive with
the weak nucleophile, ROH.

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Acetal Formation

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 Hydrolysis of Acetals

• Acetals can be hydrolyzed by addition of

dilute acid.
• The excess of water drives the equilibrium toward
the formation of the ketone or aldehyde.

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Cyclic Acetals

• Addition of a diol produces a cyclic acetal.

• The reaction is reversible.
• This reaction is used in synthesis to protect
carbonyls from reaction.
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 Carbohydrates

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Acetals As Protecting Groups

• The aldehyde requires protection.

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 Synthesis

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Oxidation of Aldehydes

Aldehydes are easily oxidized to carboxylic acids.

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 The Tollens Test

• The Tollens test involves

adding a solution of
silver–ammonia complex
(the Tollens reagent) to
the unknown compound.
• If an aldehyde is present,
its oxidation reduces
silver ion to metallic silver.

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Reduction Reagents

• Sodium borohydride, NaBH4, can reduce ketones

to secondary alcohols and aldehydes to primary
alcohols.
• Lithium aluminum hydride, LiAlH4, is a powerful
reducing agent, so it can also reduce carboxylic
acids and their derivatives.
• Hydrogenation with a catalyst can reduce the
carbonyl, but it will also reduce any double or triple
bonds present in the molecule.

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 Sodium Borohydride

• NaBH4 can reduce ketones and aldehydes, but not esters,

carboxylic acids, acyl chlorides, or amides.
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Lithium Aluminum Hydride

• LiAlH4 can reduce any carbonyl because it is a

very strong reducing agent.
• Difficult to handle
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 Catalytic Hydrogenation

• Widely used in industry

• Raney nickel is finely divided Ni powder saturated
with hydrogen gas.
• It will attack the alkene first, then the carbonyl.

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Deoxygenation of Ketones
and Aldehydes

• The Clemmensen reduction or the Wolff–Kishner

reduction can be used to deoxygenate ketones and
aldehydes.
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 Clemmensen Reduction

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Wolff–Kishner Reduction

• Form hydrazone, then heat with strong base like KOH or

potassium tert-butoxide.
• Use a high-boiling solvent: ethylene glycol, diethylene
glycol, or DMSO.
• A molecule of nitrogen is lost in the last steps of the
reaction.
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