Organic Chemistry,

9th Edition,
Global Edition
L. G. Wade, Jr.

Chapter 18
Lecture - 2
Ketones and
Aldehydes

Chad Snyder, PhD

Grace College
© 2017 Pearson Education, Ltd.
 18-7 Review of Syntheses of Ketones and Aldehydes
18-7 B Ketones and Aldehydes from Ozonolysis of Alkenes (page 926)

• The double bond is oxidatively cleaved by ozone, followed by reduction.

• Ketones and aldehydes can be isolated as products under these

conditions.
 18-7 Review of Syntheses of Ketones and Aldehydes
18-7 C Phenyl Ketones and Aldehydes: Friedel-Crafts Acylation (page 926)

• Reaction between an acyl halide and an aromatic ring will produce an

aromatic ketone.
 18-8 Synthesis of Ketones from Carboxylic Acids
First paragraph (page 929)

• Organolithiums can be prepared from alkyl or aryl halides.

 18-9 Synthesis of Ketones and Aldehydes from Nitriles
First and second paragraph (page 929 + 930)

• A Grignard reagent can attack the carbon of the nitrile.

• The imine is then hydrolyzed to form a ketone.

• A nitrile can be prepared from alkyl halide by SN2 reactions.

 18-9 Synthesis of Ketones and Aldehydes from Nitriles
First and second paragraph (page 930)

• Diisobutylaluminum hydride (DIBAL-H) is commonly used for the

reduction of nitriles.
• The DIBAL-H does not reduce the double bond.
Sample Problem 18-7 (page 929)
 18-12 Hydration of Ketones and Aldehydes
First paragraph (page 938)

• In an aqueous acidic or basic solution, a ketone or an

aldehyde is in equilibrium with its hydrate, a geminal diol
(Hydrate).
MECHANISM 18-2: Hydration of Ketones and Aldehydes
(Page 939)

In Acid:

Nucleophilic addition reaction on carbonyl group.

MECHANISM 18-2: Hydration of Ketones and Aldehydes
(Page 939)

In Base:

Nucleophilic addition reaction on carbonyl group.

 18-13 Formation of Cyanohydrins
Second paragraph (Page 941)

Hydrolysis of a cyanohydrin under acidic conditions give rise to

alpha-hydroxy acid.
 MECHANISM 18-3: Formation of Cyanohydrins
(Page 941)

Nucleophilic addition reaction on carbonyl group

 Sample Problem 18-16 (page 942)

Show how you would accomplish the following syntheses:

(a) acetophenone acetophenone cyanohydrin

 18-14 Formation of Imines
First and Second paragraph (Page 942)

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

to form an imine (Schiff base).

• It is a condensation reaction, in which two molecules joined with

the loss of a small molecule like H2O.
18-14 Formation of Imines
First paragraph (Page 944)

Examples
Sample Problem 18-19 (page 945)
 18-18 The Wittig Reaction
First paragraph (Page 954)

R Ph

C P Ph

H Ph

• A reaction between ketone or aldehyde with a phosphorus ylide.

• The Wittig reaction converts the carbonyl group into a new C═C
double bond.
• The carbon of the ylide is preferred to be not sterically hindered.
 Assignment

Use Wittig reaction to prepare the compounds in problem 18.33, p.957

You can use the necessary phosphorus ylide right away.
 Ch. 18 Exercise

39 (b, c, h, j), 47 (a, g)

Sample Problem 18-9 (page 930)