Chapter 18

Lecture
Ketones and Aldehydes

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Classes of Carbonyl
Compounds

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Chapter 18

Structure of the Carbonyl

Group

Carbon is sp2 hybridized.

CO bond is shorter, stronger, and more
polar than CC bond in alkenes.
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Chapter 18

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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Chapter 18

Ketone Nomenclature

Number the chain so that the carbonyl carbon

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

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Chapter 18

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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Chapter 18

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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Chapter 18

Solubility of Ketones and

Aldehydes
Good solvent for alcohols
Lone pair of electrons on
oxygen of carbonyl can
accept a hydrogen bond
from OH or
NH.
Acetone and
acetaldehyde are
miscible in water.

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Chapter 18

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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Chapter 18

Infrared (IR) Spectroscopy

Very strong CO stretch around 1710 cm-1 for

ketones and 1725 cm-1 for simple aldehydes
Additional CH stretches for aldehyde: Two
absorptions at 2710 cm-1 and 2810 cm-1
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Chapter 18

10

IR Spectra

Conjugation lowers the carbonyl stretching

frequencies to about 1685 cm-1.
Rings that have ring strain have higher CO
frequencies.
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Chapter 18

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Proton NMR Spectra

Aldehyde protons normally absorb between

9 and 10.
Protons of the carbon usually absorb
between 2.1 and 2.4 if there are no other
electron-withdrawing groups nearby.
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Chapter 18

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H NMR Spectroscopy

Protons closer to the carbonyl group are more deshielded.

The , and protons appear at values of that decrease with
increasing distance from the carbonyl group.

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Chapter 18

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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 carbon at 30 ppm (methyl) and 44 ppm
(methylene).
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Chapter 18

14

McLafferty Rearrangement

The net result of this rearrangement is the breaking

of the bond and the transfer of a proton from the
carbon to the oxygen.
An alkene is formed as a product of this
rearrangement through the tautomerization of the
enol.
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Chapter 18

15

Ultraviolet Spectra of Conjugated

Carbonyl Compounds

Conjugated carbonyl compounds have characteristic

-* absorption in the UV spectrum.
An additional conjugated CC increases max about
30 nm; an additional alkyl group increases it about
10 nm.
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Chapter 18

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Electronic Transitions of the CO

Small molar absorptivity

Forbidden transition occurs less frequently.
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Chapter 18

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Carbonyl n * absorptions are

very weak, and they are often
obscured by stronger absorptions.
Therefore, they are rarely as useful
as the * absorptions.

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Chapter 18

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Chapter 18

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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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Chapter 18

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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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Chapter 18

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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.
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Chapter 18

22

FriedelCrafts Reaction

Reaction between an acyl halide and an

aromatic ring will produce a ketone.
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Chapter 18

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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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Chapter 18

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HydroborationOxidation of
Alkynes

Hydroborationoxidation of an alkyne gives

anti-Markovnikov addition of water across the
triple bond.
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Chapter 18

25

Solved Problem 1
Showhowyouwouldsynthesizeeachcompoundfromstartingmaterialscontainingnomorethansix
carbonatoms.
(a)

(b)

Solution
(a) Thiscompoundisaketonewith12carbonatoms.Thecarbonskeletonmightbeassembledfrom
twosixcarbonfragmentsusingaGrignardreaction,whichgivesanalcoholthatiseasilyoxidized
tothetargetcompound.

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Chapter 18

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Solved Problem 1 (Continued)

Solution (Continued)
AnalternativeroutetothetargetcompoundinvolvesFriedelCraftsacylation.

(b) Thiscompoundisanaldehydewitheightcarbonatoms.Analdehydemightcomefromoxidation
ofanalcohol(possiblyaGrignardproduct)orhydroborationofanalkyne.IfweuseaGrignard,
therestrictiontosixcarbonstartingmaterialsmeansweneedtoaddtwocarbonstoa
methylcyclopentylfragment,endinginaprimaryalcohol.Grignardadditiontoanepoxidedoes
this.

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Chapter 18

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Solved Problem 1 (Continued)

Solution (Continued)
Alternatively,wecouldconstructthecarbonskeletonusingacetyleneasthetwocarbonfragment.
Theresultingterminalalkyneundergoeshydroborationtothecorrectaldehyde.

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Chapter 18

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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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Chapter 18

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Ketones and Aldehydes from

Nitriles

A Grignard or organolithium reagent can

attack the carbon of the nitrile.
The imine is then hydrolyzed to form a
ketone.
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Chapter 18

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Reduction of Nitriles to
Aldehydes

Aluminum hydrides can reduce nitriles to aldehydes.

Diisobutylaluminum hydride, abbreviated (i-Bu)2AlH or
DIBAL-H, is commonly used for the reduction of nitriles.
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Chapter 18

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Aldehydes from Acid

Chlorides

Lithium aluminum tri(t-butoxy)hydride is a

milder reducing agent that reacts faster with
acid chlorides than with aldehydes.

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Chapter 18

32

Lithium Dialkyl Cuprate

Reagents

A lithium dialkylcuprate will transfer one of its alkyl

groups to the acid chloride.
Grignards and organolithiums cannot do this
reaction.
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Chapter 18

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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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Chapter 18

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The Wittig Reaction

The Wittig reaction converts the carbonyl

group into a new CC double bond where no
bond existed before.
A phosphorus ylide is used as the nucleophile
in the reaction.
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Chapter 18

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Preparation of Phosphorus Ylides

Prepared from triphenylphosphine and an

unhindered alkyl halide.
Butyllithium then abstracts a hydrogen from
the carbon attached to phosphorus.
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Chapter 18

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Mechanism of the Wittig Reaction

Betaine formation

Oxaphosphetane formation

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Chapter 18

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Mechanism for Wittig

The oxaphosphetane will collapse, forming

carbonyl (ketone or aldehyde) and a molecule
of triphenyl phosphine oxide.
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Chapter 18

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Plan a Wittig synthesis so that the less

hindered end of the double bond comes
from the ylide. Remember that the ylide
is made by SN2 attack of
triphenylphosphine on an unhindered alkyl
halide, followed by deprotonation.

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Chapter 18

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Solved Problem 2
ShowhowyouwoulduseaWittigreactiontosynthesize1phenyl1,3butadiene.

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Chapter 18

40

Solved Problem 2 (Continued)

Solution (Continued)
ThismoleculehastwodoublebondsthatmightbeformedbyWittigreactions.Thecentraldoublebond
couldbeformedineitheroftwoways.Bothofthesesyntheseswillprobablywork,andbothwill
produceamixtureofcisandtransisomers.

Youshouldcompletethissolutionbydrawingoutthesynthesesindicatedbythisanalysis
(Problem1816).
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Chapter 18

41

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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Chapter 18

42

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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Chapter 18

43

Base-Catalyzed Hydration of
Carbonyls

The hydroxide ion attacks the carbonyl

group.
Protonation of the intermediate gives the
hydrate.
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Chapter 18

44

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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Chapter 18

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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 CN bond in place of the carbonyl
group.
Optimum pH is around 4.5.
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Chapter 18

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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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Chapter 18

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Imine formation is one of the important

mechanisms in this chapter. It is more
easily remembered as consisting of
two simple mechanisms:
1. acid-catalyzed nucleophilic
addition to the carbonyl, and
2. acid-catalyzed dehydration (as
with an alcohol).

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Chapter 18

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Other Condensations with Amines

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Chapter 18

49

Formation of Acetals

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Chapter 18

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Mechanism for Hemiacetal

Formation

Must be acid-catalyzed.
Adding H+ to carbonyl makes it more reactive
with weak nucleophile, ROH.
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Chapter 18

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Acetal Formation

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Chapter 18

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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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Chapter 18

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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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Chapter 18

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Acetals as Protecting Groups

O
H
O

HO

OH

Hydrolyze easily in acid; stable in base

Aldehydes are more reactive than ketones.

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Chapter 18

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Formation of an acetal (or hemiacetal)

does not alter the oxidation state of the
carbonyl carbon atom. In an acetal or
hemiacetal, the carbonyl carbon atom is
the one with two bonds to oxygen.

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Chapter 18

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Reaction and Deprotection

O

O
H

O
1) NaBH4
2) H3O+

H
OH

The acetal will not react with NaBH4, so only

the ketone will get reduced.
Hydrolysis conditions will protonate the
alcohol and remove the acetal to restore the
aldehyde.
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Chapter 18

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Oxidation of Aldehydes

Aldehydes are easily oxidized to carboxylic acids.

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Chapter 18

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The Tollens Test

The Tollens test involves
adding a solution of
silverammonia 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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Chapter 18

59

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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Chapter 18

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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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Chapter 18

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Lithium Aluminum Hydride

OH

O
R

R(H)

LiAlH4
ether

R(H)

aldehyde or ketone

LiAlH4 can reduce any carbonyl because it is a very strong

reducing agent.
Difficult to handle

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Chapter 18

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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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Chapter 18

63

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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Chapter 18

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Clemmensen Reduction

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Chapter 18

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