Organic Chemistry,
8th Edition
L. G. Wade, Jr.
Chapter 18
Lecture
Aldehydes & Ketones: Part I
Overview
Classes of Carbonyl Compounds
Structure of Carbonyl Group
Nomenclature of Ketones & Aldehydes
Physical Properties
IR & NMR Spectroscopy
Preparing Ketones & Aldehydes: A
Review
2
Classes of Carbonyl Compounds
© 2013 Pearson Education, Inc. Chapter 9 3
Structure of the Carbonyl Group
Carbon is sp2 hybridized.
C═O bond is shorter, stronger, and more polar
than C═C bond in alkenes.
© 2013 Pearson Education, Inc. Chapter 18 4
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.
© 2013 Pearson Education, Inc. Chapter 18 5
Ketone Nomenclature
Number the chain so that the carbonyl carbon has
the lowest number.
Replace the alkane -e with -one.
© 2013 Pearson Education, Inc. Chapter 18 6
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.
© 2013 Pearson Education, Inc. Chapter 18 7
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.
© 2013 Pearson Education, Inc. Chapter 18 8
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.
Common Names for Ketones
Named as alkyl attachments to —C═O
Use Greek letters instead of numbers.
Historical Common Names
© 2013 Pearson Education, Inc. Chapter 9 11
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.
© 2013 Pearson Education, Inc. Chapter 18 12
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.
© 2013 Pearson Education, Inc. Chapter 18 13
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.
© 2013 Pearson Education, Inc. Chapter 18 14
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
© 2013 Pearson Education, Inc. Chapter 18 15
IR Spectra
Conjugation lowers the carbonyl stretching
frequencies to about 1685 cm-1.
Rings that have ring strain have higher C═O
frequencies.
© 2013 Pearson Education, Inc. Chapter 18 16
Proton NMR Spectra
Aldehyde protons normally absorb between
d9 and d10.
Protons of the α carbon usually absorb between
d2.1 and d2.4 if there are no other electron-
withdrawing groups nearby.
© 2013 Pearson Education, Inc. Chapter 18 17
1
H NMR Spectroscopy
Protons closer to the carbonyl group are more deshielded.
The a, b , and g protons appear at values of d that decrease with
increasing distance from the carbonyl group.
© 2013 Pearson Education, Inc. Chapter 18 18
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.
© 2013 Pearson Education, Inc. Chapter 18 20
Preparing Aldehydes & Ketones: A
Review of Past Reactions
Grignards as Source for Aldehydes &
Ketones
Ozonolysis of Alkenes
Friedel-Crafts Reaction
Hydration of Alkynes
Hydroboration-Oxidation of Alkynes
Chapter 18 21
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.
© 2013 Pearson Education, Inc. Chapter 18 22
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.
© 2013 Pearson Education, Inc. Chapter 18 23
Ozonolysis of Alkenes
The double bond is oxidatively cleaved by ozone
followed by reduction.
Ketones and aldehydes can be isolated as products
under these conditions.
© 2013 Pearson Education, Inc. Chapter 18 24
Friedel–Crafts Reaction
Reaction between an acyl halide and an aromatic
ring will produce a ketone.
© 2013 Pearson Education, Inc. Chapter 18 25
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.
© 2013 Pearson Education, Inc. Chapter 18 26
Hydroboration–Oxidation of Alkynes
Hydroboration–oxidation of an alkyne gives anti-
Markovnikov addition of water across the triple
bond.
© 2013 Pearson Education, Inc. Chapter 18 27
Solved Problem 1
Show how you would synthesize each compound from starting materials containing no more than six
carbon atoms.
(a) (b)
Solution
(a) This compound is a ketone with 12 carbon atoms. The carbon skeleton might be assembled from
two six-carbon fragments using a Grignard reaction, which gives an alcohol that is easily oxidized
to the target compound.
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Solved Problem 1 (Continued)
Solution (Continued)
An alternative route to the target compound involves Friedel–Crafts acylation.
(b) This compound is an aldehyde with eight carbon atoms. An aldehyde might come from oxidation
of an alcohol (possibly a Grignard product) or hydroboration of an alkyne. If we use a Grignard,
the restriction to six-carbon starting materials means we need to add two carbons to a
methylcyclopentyl fragment, ending in a primary alcohol. Grignard addition to an epoxide does
this.
© 2013 Pearson Education, Inc. Chapter 9 29
Solved Problem 1 (Continued)
Solution (Continued)
Alternatively, we could construct the carbon skeleton using acetylene as the two-carbon fragment.
The resulting terminal alkyne undergoes hydroboration to the correct aldehyde.
© 2013 Pearson Education, Inc. Chapter 9 30
