Chapter 18 Ketones and Aldehydes

Nomenclature
o Ketones have priority over alcohols
Find the longest chain with the carbonyl in it.
Name the parent and replace the e with one
Say where the carbonyl is.

When the ketone is not the high-priority group, you call the
carbonyl oxo to name it.
Common names: Name the two pieces coming off the
carbonyl and call it ketone

o Aldehydes have priority over ketones

Find the longest chain with the carbonyl at the end.
Name the parent and replace the e with al.

Synthesis of ketones and aldehydes

o Oxidation of alcohols
1 ROH
2 ROH
3 ROH

Chromic Acid
RCOOH
Ketone
NR

o Ozonolysis of alkenes

KMnO4
RCOOH
Ketone
NR

PCC
RCHO
Ketone
NR

Swern
RCHO
Ketone
NR

 See Chapter 8 for review

o Friedel-Crafts Acylation

See Chapter 17 for review

o Hydration of alkynes
Acid-catalyzed

Hydroboration-oxidation

See Chapter 8 for review

o Synthesis from carboxylic acids and acid chlorides
Acids are first converted to acid chlorides.

Acid chlorides are reduced to aldehydes with LiAlH(OtBu) 3

LiCuR2
o LiCuR2 is like a specialty version of a Grignard that only replaces
the Cl of acid chlorides.

Wittig Reactions
o Overall reaction: turn a carbonyl into a carbon-carbon double
bond.
The carbon of the alkyl halide replaces the oxygen of the
carbonyl.

o Step one: Triphenylphosphine attacks an alkyl halide

o Step two: Grignard deprotonates to form the ylide

Whats an ylide?
An ylide is when you have two atoms next to each
other where one has a negative charge, the other
has a positive charge, and they both have full octets.

o Step 3: ylide attacks the carbonyl

o Step 4: O- forms bond with P+

o Ring collapses fun with arrows

o Considerations: You want alkyl halide to be methyl or primary because

they are best for SN2

Hydration
o Acid-catalyzed

o Base-catalyzed

o Rates
This reaction doesnt happen to a large degree with most
ketones
It happens a little more with aldehydes
Keq for formaldehyde is 40
Formation of Cyanohydrins
o HCN is a toxic gas, so most often it is made in situ from excess
NaCN and HCl.
o Step one: cyanide ion attacks the carbonyl.

o Step two: protonation

o Things you can do with cyanohydrins.

Catalytic hydration

Hydrolysis

Formation of imines
o Overall: The nitrogen replaces the oxygen of the carbonyl,
forming a carbon-nitrogen double bond.
It should be mildly acidic; pH between 4 and 5.

o Mr. Baker said that you are not responsible for the mechanism,
but here it is in case you want to look at it.
o Step one: protonation of the carbonyl

o Step two: Amine attacks the activated carbonyl

o Step three: Deprotonation

o Step four: Protonation of hydroxyl

o Step five: Loss of water

o Step six: Deprotonation

Formation of acetals
o You could call an acetal a geminal diether
A hemiacetal is what you have when youre halfway there.
It is one hydroxyl and one alkoxy group coming off the
same carbon.
o Step one: protonation of the carbonyl

o Step two: the alcohol attacks the activated carbonyl

o Step three: deprotonation to give the hemiacetal

o Step four: Protonation of the hydroxyl

o Step five: water falls off

o Step six: another alcohol adds

o Step seven: deprotonation gives the acetal

Removing acetals
o Use very dilute acid
o The mechanism of hydrolysis of an acetal is just the same thing
going backwards.
Acetals and hemiacetals in sugars
o Sugars exist in their cyclic forms as hemiacetals
The carbon which is the hemiacetal or acetal is called the
anomeric carbon.
When the OH is up, its Beta; when its down, its alpha.

o When they link up to become polysaccharides, they become

acetals.

o Something you dont need to know for this class, but the MCAT
expects you to know:
Sugars that differ by only one chiral center are called
epimers.

Protecting groups
o Requirements of a good protecting group
Easy to put on
Nonreactive under the reaction conditions
Easily removable
Oxidation of aldehydes
o Aldehydes are oxidized to carboxylic acids by KMnO4 and chromic
acid
Reductions of ketones and aldehydes
o The following reductions which have already been seen work on
ketones and aldehydes:
NaBH4

LiAlH4

H2/ Raney
Ni

Zn(Hg)/HC
l (aq)

N2H4/base

Ketone

2 ROH

2 ROH

2 ROH

Alkane

Alkane

Aldehyde

1 ROH

1 ROH

1 ROH

Alkane

Alkane