Pre-Reading Problem

Given the formal chemical names of the alcohols below, and suggest a
method for preparing each of the alcohols above using chemistry you have
already seen in this course.
 Functional Groups 2 - Block Overview

In ‘Functional Groups 1’ we covered the reactions of

• Alkenes and Alkynes
• Aromatic Compounds
• Alkyl Halides
‘Functional Groups 2’ will focus on the reactivity of
• Alcohols, Aldehydes and Ketones.
• Carboxylic Acids and their Derivatives
• Amines
You will also be introduced to the chemistry of important
biomolecules, such as sugars, amino acids and proteins.
Recall: Alcohols can be prepared by:
Acid catalysed addition of H2O (Block 4)

“rich get richer” Markovnikov

Addition

Electrophilic Addition
1.3.2 (b) Hydroboration - Oxidation

anti-Markownikoff
Addition
Mechanism:
Electrophile – “BH3”

Electrophilic Addition
(followed by oxidation)
Designing a synthetic route – appropriate choice of reagents

Starting from 1-butane we can make either 1-butanol or 2-

butanol depending on the choice of reagents.

For symmetrical alkenes (eg but-2-ene) both reagents give the

same product.
The remaining methods for the preparation of alcohols are
concerned with the addition of a nucleophile to a carbonyl group.

General mechanism:

Nu- H3O+
Nu Nu H

Nu- = H- (hydride anion, from NaBH4 or LiAlH4

= R- (carbanion, from Grignard reagent RMgX)

Nucleophilic Addition
1.3.3 Reduction of an aldehyde, a ketone or an ester
NaBH4 (mild) or LiAlH4 (strong) as H- source, followed by H3O+.
Examples:

Aldehyde – 1o alcohol

Ketone – 2o alcohol

Ester – 1o alcohol

Note: 3o alcohols cannot be prepared using this method.

1.3.4 Addition of a Grignard Reagent
Recall: Grignard reagents are prepared from the corresponding alkyl
halide.

(a) Addition to methanal (HCHO)

methanal – 1o alcohol
(b) Addition to aldehydes other than methanol

aldehyde – 2o alcohol

(c) Addition to ketones

ketone – 3o alcohol
(d) Addition to esters and acyl chlorides (Unit 5)

Ester or acid chloride (2 equiv. of Grignard) – 3o alcohol

with 2 groups the same.
Practice Question:
How would you prepare the following from starting materials
with no more than three carbons?
Preparation of Alcohols (Summary)

Alcohol Prepared Starting Material Reagent Required

Primary (1o) 1o alkyl halide -OH

1-alkene (terminal alkene) B2H6 then H2O2/-OH

Aldehyde NaBH4 or LiAlH4
Ester LiAlH4
methanal Grignard Reagent
Secondary (2o) 2o alkyl halide -OH

1-alkene (terminal alkene) H+/H2O eg dilute H2SO4

Internal alkene (eg 2-alkene) H+/H2O eg dilute H2SO4
Ketone NaBH4 or LiAlH4
Aldehyde Grignards Reagent
Tertiary (3o) 3o alkyl halide H2O
trisubstituted alkene H+/H2O eg dilute H2SO4
ketone, ester, acyl choride Grignard Reagent