Chapter 19

Ketones and Aldehydes

Review of Concepts
Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of
Chapter 19. Each of the sentences below appears verbatim in the section entitled Review of Concepts and
Vocabulary.

The suffix “_____” indicates an aldehydic group, and the suffix “_____” is used for ketones.
The electrophilicity of a carbonyl group derives from _____________ effects, as well as __________ effects.
A general mechanism for nucleophilic addition under basic conditions involves two steps
1) nucleophilic attack
2) ________________
The position of equilibrium is dependent on the ability of the nucleophile to function as a _______________.
In acidic conditions, an aldehyde or ketone will react with two molecules of alcohol to form an .
The reversibility of acetal formation enables acetals to function as _______________ groups for ketones or
aldehydes. Acetals are stable under strongly _______ conditions.
In acidic conditions, an aldehyde or ketone will react with a primary amine to form an .
In acidic conditions, an aldehyde or ketone will react with a secondary amine to form an .
In the olff-Kishner reduction, a hydrazone is reduced to an _________ under strongly basic conditions.
of acetals, imines, and enamines under acidic conditions produces ketones or
aldehydes.
In acidic conditions, an aldehyde or ketone will react with two equivalents of a thiol to form a
.
When treated with Raney nickel, thioacetals undergo desulfurization to yield a ______________ group.
When treated with a hydride reducing agent, such as lithium aluminum hydride (LiAlH4) or sodium
borohydride (NaBH4), aldehydes and ketones are reduced to _______________.
The reduction of a carbonyl group with LiAlH4 or NaBH4 is not a reversible process, because hydride does
not function as a ____________________.
When treated with a rignard reagent, aldehydes and ketones are converted into alcohols, accompanied by
the formation of a new ___________ bond.
rignard reactions are not reversible, because carbanions do not function as __________________.
When treated with hydrogen cyanide (HCN), aldehydes and ketones are converted into .
For most aldehydes and unhindered ketones, the equilibrium favors formation of the __________________.
The ittig reaction can be used to convert a ketone to an _________.
A Baeyer- illiger o idation converts a ketone to an __________ by inserting _____________________
next to the carbonyl group. Cyclic ketones produce cyclic esters called .

Review of Skills
Fill in the blanks and empty boxes below. To verify that your answers are correct, look in your textbook at
the end of Chapter 19. The answers appear in the section entitled SkillBuilder Review.

19.1 Naming Aldehydes and Ketones

www.MyEbookNiche.eCrater.com
 CHAPTER 19 703

19.2 Drawing the Mechanism of Acetal ormation

19.3 Drawing the Mechanism of Imine ormation

19.4 Drawing the Mechanism of Enamine ormation

19.5 Drawing the Products of a Hydrolysis Reaction

DRAW THE EX PECTED STEP 1 - IDENTIFY THE STEP 2 - IDENTIFY THE STEP 3 - DETERMINE THE
PRODUCTS W HEN THE BOND(S) EXPECTED TO CARBON ATOM THAT W ILL IDENTITY OF THE OTHER
FOLLOW ING COMPOUND IS UNDERGO CLEAVAGE BECOME A CARBONYL GROUP FRAGMENT(S)
TREATED W ITH AQUEOUS ACID

www.MyEbookNiche.eCrater.com
704 CHAPTER 19

19.6 Predicting the Major Product of a ittig or H E Reaction

EX AMPLE STEP 1 - IDENTIFY THE STEP 2 - DETERMINE STEP 3 - DRAW THE
NUCLEOPHILE AND W HETHER THE W ITTIG ALKENE PRODUCT W ITH
O ELECTROPHILE REAGENT IS STABILIZED THE APPROPRIATE
STEREOCHEMISTRY
CH3

H
Ph3P C
CH2CH3

?
19.7 Proposing a Synthesis

Review of Reactions
Identify the reagents necessary to achieve each of the following transformations. To verify that your
answers are correct, look in your textbook at the end of Chapter 19. The answers appear in the section
entitled Review of Reactions.

www.MyEbookNiche.eCrater.com
 CHAPTER 19 705

Common Mistakes to Avoid

This chapter covers many reactions, including the formation of acetals:

This reaction is covered in the context of the reactivity of ketones and aldehydes. The same reaction does
not occur for other compounds containing a carbonyl group, such as esters:

Students often make this mistake, assuming that acetal formation will work for esters, just as it does for
ketones. It does not. This is a common mistake, and it should be avoided.
As another example of a reaction that is often applied in the wrong context, consider the Wittig reaction.

Once again, Chapter 19 covers this reaction in the context of the reactivity of ketones and aldehydes. You
cannot assume that the same reaction will occur for other compounds containing a carbonyl group, such as
esters:

Students often make this type of mistake, by applying a reaction outside of the scope in which it was
discussed. Try to avoid doing this. Whenever we cover a reaction that applies to ketones and aldehydes,
you cannot assume that it will apply to esters (or any other functional group for that matter).

Useful reagents
The following is a list of reagents encountered in this chapter:

Reagents Type of Reaction Description

Conversion of a carbonyl group to a hydrate.
This process is only efficient for
H3O+ Hydrate formation formaldehyde and some simple aldehydes.
For ketones, the equilibrium generally does
not favor formation of the hydrate.

H+ , 2 ROH, Acetal formation Conversion of an aldehyde or ketone into an

acetal. The acetal group can be used to

www.MyEbookNiche.eCrater.com
706 CHAPTER 19

H2O) protect aldehydes and ketones. The acetal

group is stable to basic conditions, but is
removed when subjected to aqueous acidic
conditions to regenerate the carbonyl group (a
process called hydrolysis).
Ethylene glycol can be used to convert an
aldehyde or ketone into an acetal. The acetal
H+ , HOCH2CH2OH, group can be used to protect aldehydes and
Cyclic acetal
ketones. The acetal group is stable to basic
H2O formation
conditions, but is removed when subjected to
aqueous acidic conditions to regenerate the
carbonyl group (a process called hydrolysis).
H+ , HSCH2CH2SH, Cyclic thioacetal Ethylene thioglycol can be used to convert an
H2O) formation aldehyde or ketone into a cyclic thioacetal.
Converts a thioacetal (or cyclic thioacetal) to
Raney Nickel Desulfurization
an alkane.
Converts an aldehyde or ketone into an imine.
H+ , RNH2, The imine group is removed when subjected
Imine formation
H2O) to aqueous acidic conditions to regenerate the
carbonyl group (a process called hydrolysis).
Converts an aldehyde or ketone into an
+
H , R2NH, enamine. The enamine group is removed
Enamine formation when subjected to aqueous acidic conditions
H2O) to regenerate the carbonyl group (a process
called hydrolysis).
H+ , NH2OH,
Oxime formation Converts an aldehyde or ketone into an oxime.
H2O)
H+ , NH2NH2, Converts an aldehyde or ketone into a
Hydrazone formation
H2O) hydrazone.
Wolff-Kishner
NaOH, H2O, heat Reduces a hydrazone to an alkane.
reduction
1) LiAlH4
Reduction Reduces an aldehyde or ketone to an alcohol.
2) H2O
When an aldehyde or ketone is treated with a
1) RMgBr rignard reagent (followed by water work-
rignard reaction up), a carbon-carbon bond-forming reaction
2) H2O occurs, giving an alcohol that exhibits the
newly formed C-C bond.
Cyanohydrin Converts an aldehyde or ketone into a
HCN, KCN
formation cyanohydrin.
When an aldehyde or ketone is treated with a
Wittig reagent, a carbon-carbon bond-forming
reaction occurs, giving an alkene that exhibits
the newly formed C=C bond in the location of
Wittig reaction
the former carbonyl group. If R is a simple
alkyl group, such as methyl or ethyl, then the
(Z) alkene is generally observed to be the
major product.

www.MyEbookNiche.eCrater.com
 CHAPTER 19 707

A stabilized Wittig reagent that will react with

Wittig reaction an aldehyde or ketone to give the (E) alkene
as the major product.

O O A HWE reagent functions like a stabilized

HWE reaction
Wittig reagent. It will react with an aldehyde
MeO P (Horner-Wadsworth-
OMe or ketone to give the (E) alkene as the major
MeO Emmons)
product.
Converts a ketone into an ester (via insertion
Baeyer- illiger of an oxygen atom). Converts an aldehyde
RCO3H
oxidation into a carboxylic acid (via insertion of an
oxygen atom).

Solutions
19.1. methyl groups (two at C2 and two at C5), giving the
(a) We begin by identifying the longest chain that following name:
includes the carbon atom of the carbonyl group. In this
case, the parent is a chain of six carbon atoms, with the
carbonyl group at C1, so the parent is hexanal. Next, we
identify the substituents. There are four: two methyl
groups (both at C2) and two bromine atoms (both at C5).
Finally, we assemble the substituents alphabetically,
giving the following name:
(d) We begin by identifying the longest chain that
includes the carbon atom of the carbonyl group. In this
case, the parent is a chain of five carbon atoms, with the
carbonyl group at C1, so the parent is pentanal. Next, we
identify the substituents. There is only one substituent: a
propyl group at C2, giving the following name:

(b) We begin by identifying the longest chain that

includes the carbon atom of the carbonyl group. In this
case, the parent is a chain of six carbon atoms, with the
carbonyl group at C2, so the parent is 2-hexanone. Next,
we identify the substituents. There are three, all of
which are methyl groups, located at C3, C4 and C5. We (e) A cyclic compound containing an aldehyde adjacent
then assign a configuration to each of the chiral centers, to the ring is named as a cycloalkane carbaldehyde. In
giving the following name: this case, the aldehyde group is connected to a four-
membered ring (cyclobutane), giving the following
name:

(c) We begin by identifying the parent. In this case, the

carbonyl group is part of a five-membered ring, so the 19.2.
parent is cyclopentanone. In a cyclic ketone, the (a) The name indicates that the parent (cyclohexanone) is
carbonyl group is at C1 (by definition). Next, we a six-membered ring, with a carbonyl group incorporated
identify the substituents. There are four, all of which are in the ring (a cyclic ketone). There are three

www.MyEbookNiche.eCrater.com