CHEMISTRY GRADE 11

O
RCH2OH
PCC
R CH
≡ C6H5NHCrO3Cl
N CrO Cl
A 1° alcohol CH2Cl2 An aldehyde 3
H
PCC = Pyridinium chlorochromate

Example:

O
PCC
CH3CH2CH2CH2OH CH3CH2CH2 CH
CH2Cl2 Butanal
1-butanol

     

The partially positive charge on the carbonyl carbon is the cause of the most common
reaction theme of the carbonyl group, the addition of a nucleophile (Nu:) to form a
tetrahedral carbonyl addition intermediate.

R δ δ O
+ C O Nu C
Nu R
R
R
Tetrahedral carbonyl
addition intermediate
a. Addition
i. Addition of Grignard Reagents to Aldehydes and Ketones
The addition of carbon nucleophiles is the most important type of nucleophilic
addition to a carbonyl group because these reactions form new carbon–carbon
bonds. The Grignard reagent is an alkylmagnesium halide.
Mg
R X R: MgX R = alkyl or aryl
Alkyl halide ether Grignard reagent
(X = Cl, Br, I)
Example:

178 UNIT 6
 Aldehydes and Ketones

Mg
CH3CH2Br CH3CH2: MgBr
Et2O

1. Addition to Formaldehyde Gives a 1°Alcohol

Treatment of a Grignard reagent with formaldehyde, followed by hydrolysis

in aqueous acid, gives a primary alcohol:
Example:
O O MgBr OH
Et2O H3O+
CH3CH2-MgBr + H C H CH3CH2 CH2 CH3CH2 CH2
1- propanol
(1° alcohol)

2. Addition to an Aldehyde (Except Formaldehyde) Gives a 2°Alcohol

Treatment of a Grignard reagent with any aldehyde other than formaldehyde,
followed by hydrolysis in aqueous acid, gives a secondary alcohol:
Example:
O O MgBr
Et2O OH
CH3CH2-MgBr + H3C C H H3O+
CH3CH2 CH CH3 CH3CH2 CH CH3
2- butanol
(2° alcohol)
3. Addition to a Ketone Gives a 3°Alcohol
Treatment of a Grignard reagent with a ketone, followed by hydrolysis in
aqueous acid, gives a tertiary alcohol.
Example:
O O MgBr
Et2O OH
CH3CH2-MgBr + H3O+
H3C C CH3 CH3CH2 C CH3 CH3CH2 C CH3
CH3 CH3
2- methyl-2- butanol
(3° alcohol)

ii. Addition of Alcohol: formation of Acetals

The addition of a molecule of alcohol to the carbonyl group of an aldehyde or
a ketone forms a hemiacetal (a half-acetal). This reaction is catalyzed by both
acid and base: Oxygen adds to the carbonyl carbon and hydrogen adds to the
carbonyl oxygen.

UNIT 6 179
 CHEMISTRY GRADE 11

Example:
O OH
H+ or OH-
H3C C CH3 + HOCH2CH3 H3C C OCH2CH3
CH3
A hemiacetal
The functional group of a hemiacetal is a carbon bonded to an −OH group and an −OR
or −OAr group:
from an
aldehyde OH OH from a
ketone
R C OR' R C OR'

H R''

Hemiacetals
Hemiacetals can react further with alcohols to form acetals plus a molecule of water.
This reaction is acid catalyzed.
Example:

OH OCH2CH3
H3C C OCH2CH3 H+
+ HOCH2CH3 H3C C OCH2CH3 + H2O
CH3 CH3
A hemiacetal A diethyl acetal

The functional group of an acetal is a carbon bonded to two −OR or −OAr groups:

from an
aldehyde OR' OR' from a
ketone
R C OR' R C OR'

H R''

Acetals

180 UNIT 6
 Aldehydes and Ketones

a. Oxidation
i. Oxidation of Aldehydes to Carboxylic Acids
Aldehydes are oxidized to carboxylic acids by a variety of common oxidizing
agents, including chromic acid and molecular oxygen. In fact, aldehydes are one
of the most easily oxidized of all functional groups.
Example:
O O
H2CrO4
H OH
Hexanal Hexanoic acid

When Tollens’ reagent (Ag(NH3)2+) is added to an aldehyde, the aldehyde is

oxidized to a carboxylic anion, and Ag+ is reduced to metallic silver. If this reaction
is carried out properly, silver precipitates as a smooth, mirror like deposit—hence
the name silver-mirror test:

O O
+ NH3, H2O
R C H + 2Ag(NH3)2 R C O + 2Ag + 4NH3
Precipitate as
silver mirror

Tollens’ reagent does not react with Aldehydes, which can be used to distinguish
aldehydes from ketones. Nowadays, Ag+ is rarely used for the oxidation of
aldehydes, what do you think the reason?

ii. Oxidation of Ketones to Carboxylic Acids

Ketones are much more resistant to oxidation than are aldehydes. For example,
ketones are not normally oxidized by chromic acid or potassium permanganate.
Ketones undergo oxidative cleavage, via their enol form, by potassium dichromate
and potassium permanganate at higher temperatures and by higher concentrations
of nitric acid, HNO3.

UNIT 6 181
 CHEMISTRY GRADE 11

Example:
O OH O

HNO3 HO
OH

O
Cyclohexanone Cyclohexanone Hexanedioic acid
(keto form) (enol form) (adipic acid)

c. Reduction
Aldehydes are reduced to primary alcohols and ketones to secondary alcohols:
O O OH
Reduction Reduction
R C H R CH2OH R C R' R CH R'
An aldehyde A primary A ketone A secondary
alcohol alcohol

i. Catalytic Reduction
The carbonyl group of an aldehyde or a ketone is reduced to a hydroxyl group
by hydrogen in the presence of a transition metal catalyst, most commonly finely
divided palladium, platinum, nickel, or rhodium.
Example:
O OH

+ H2 Pt

25 °C, 2 atm
Cyclohexanone Cyclohexanol
ii. Metal Hydride Reductions
By far the most common laboratory reagents used to reduce the carbonyl group of
an aldehyde or a ketone to a hydroxyl group are sodium borohydride and lithium
aluminum hydride. Each of these compounds behaves as a source of hydride ion,
a very strong nucleophile.
H H
Na+ H B H Li+ H Al H H
H H
Sodium borohydride Lithium aluminum Hydride ion
hydride

182 UNIT 6
 Aldehydes and Ketones

Lithium aluminum hydride is a very powerful reducing agent; it rapidly reduces

not only the carbonyl groups of aldehydes and ketones, but also those of carboxylic
acids and their functional derivatives. Sodium borohydride is a much more
selective reagent, reducing only aldehydes and ketones rapidly.
Example:

O
1. LIAlH4, diethyl ether
CH3(CH2)5CH CH3(CH2)5CH2OH
Heptanal 2. H2O 1-Heptanol

Assessment
You should assess each student’s work throughout the section. Using your students’
performance list, record how every student participates during discussions,
presentations and explanations. Using questions from the suggested exercises or your
own, give class works and home works. Check their exercise books and evaluate how
the students perform in answering the questions. You can also give them test on the
section. Help students working below the minimum requirement level by giving them
extra activities so that they will catch up with the rest of the class.

³ Answers to Exercise 6.6

1. a. False b. False c. False

O CH3 O O
2. CH3 C CH2 CH3 H3C CH C H CH3 CH2 CH C H
Butanone 2-Methylpropanal Butanal
3.
O O
OH O

a. Cl
b. c.
H OH
1-Chloro-2-propanone
3-Hydroxybutanal 4-Hydroxy-4-methyl-2-pentanone

4. a. hexan-3-one b. hexanal
5. Formaldehyde (Ethanal)

UNIT 6 183