John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 10
Organohalides

Paul D. Adams University of Arkansas

What Is an Organohalide?

An organic compound containing at least one

carbon-halogen bond (C-X)
X (F, Cl, Br, I) replaces H
Can contain many C-X bonds
Properties and some uses
Fire-resistant solvents
Refrigerants
Pharmaceuticals and precursors

Why this Chapter?

Reactions involving organohalides are less

frequently encountered than other organic
compounds, but reactions such as
nucleophilic substitutions/eliminations that
they undergo will be encountered
Alkyl halide chemistry is model for
mechanistically similar but more complex
reactions

10.1 Naming Alkyl Halides

Find longest chain, name it as parent chain

(Contains double or triple bond if present)
Number from end nearest any substituent (alkyl
or halogen)

Naming if Two Halides or Alkyl Are

Equally Distant from Ends of Chain

Begin at the end nearer the substituent having its

name first in the alphabet

10.1 Structure of Alkyl Halides

C-X bond is longer as you go down periodic table

C-X bond is weaker as you go down periodic table
C-X bond is polarized with slight positive charge on
carbon and slight negative charge on halogen

10.2 Preparing Alkyl Halides from

Alkanes: Radical Halogenation

Alkyl halide from

addition of HCl,
HBr, HI to
alkanes

Preparing Alkyl Halides from

Alkanes: Radical Halogenation

Alkane + Cl2 or Br2, heat or light replaces C-H with C-X but

gives mixtures

Hard to control
Via free radical mechanism
It is usually not a good idea to plan a synthesis that uses
this method

Radical Halogenation of Alkanes

If there is more than one type of hydrogen in an alkane,

reactions favor replacing the hydrogen at the most highly
substituted carbons (not absolute)

Relative Reactivity

Based on quantitative analysis of reaction products, relative

reactivity is estimated
Order parallels stability of radicals
Reaction distinction is more selective with bromine than
chlorine

Chlorination vs. Bromination

10.3 Preparing Alkyl Halides from

Alkenes: Allylic Bromination

N-bromosuccinimide (NBS) selectively brominates allylic

positions (due to lower E resulting from resonance)
Requires light for activation
A source of dilute bromine atoms

Allylic Stabilization

Allyl radical is delocalized

More stable than typical alkyl radical by 40 kJ/mol (9
kcal/mol)
Allylic radical is more stable than tertiary alkyl radical

10.4 Stability of the Allyl Radical:

Resonance Revisited

Three electrons are delocalized over three carbons

Spin density surface shows single electron is dispersed

Effects of Resonance
Allylic bromination of unsymmetrical alkenes usually produces mixed
products.
Rxn at less hindered primary is favored.
Also, in general, more highly-substituted alkenes are more stable.
Br

NBS

Br

hv, CCl4
minor

major

10.5 Preparing Alkyl Halides from

Alcohols

Reaction of tertiary C-OH with HX is fast and effective

Add HCl or HBr gas into ether solution of 3alcohol
1and 2alcohols react very slowly and often rearrange,
so alternative methods are used (Ch. 11)

10.6 Organometallic Reagents

for Alcohol Synthesis
A covalent bond between carbon (C) and a metal (M) makes the C nucleophilic.

C
-

M
+

C
-

Li
+

C
-

Mg
+

Types of Organometallic
Coupling Reagents/Rxns

Grignard Reagents
Alkyllithium Reagents
Gilman Reagents
Suzuki-Miyaura Reaction

10.6 Reactions of Alkyl Halides:

Grignard Reagents

Reaction of RX with Mg in ether or THF

Product is RMgX an organometallic compound (alkyl-metal
bond)
R is alkyl 1, 2, 3, aryl (aromatic), alkenyl (vinylic)
X = Cl < Br < I

Reagent Synthesis

Formation of Grignard Reagent:

R X
Br

Mg

Mg

Ether

R MgX

Ether

MgBr

Formation of Alkyllithium Reagent:

R X

Br

2 Li

2 Li

R Li

Li

Li+- X

Li+- Br

Organometallic reagent
mechanism

The metals in both Grignard reagents and alkyllithium

reagents turn the attached R group into a nucleophile,
that can then attack an electrophilic carbon (e.g.,
carbonyl)

Examples

*We will return to these reactions after discussing alcohols and carbonyls

Limitations/Scope of Grignard
and Alkyllithium Reagents

Both are good nucleophiles, but will act as bases

if H+ available in solution:
MgBr

H2O

HOMgBr

In the presence of multiple bonds with a strong

EN atom, will attack as nucleophile:

C=O, C=N, CN, S=O, N=O

10.7 Organometallic Coupling

Reactions

Alkyllithium (RLi) forms from RBr and Li metal

RLi (primary, secondary or tertiary alkyl, aryl or vinyl R group)
reacts with copper iodide to give lithium dialkylcopper (Gilman
reagents)

Utility of Organometallic Coupling

in Synthesis

Lithium dialkylcopper (Gilman) reagents react with alkyl

halides to give alkanes
Aryl and vinyl organometallics also effective

Suzuki-Miyaura Reaction

Coupling rxn of aromatic or vinyl substituted boronic acid

with aromatic or vinyl substituted organohalide in
presence of base and palladium catalyst.
Widely used today in pharmaceutical industry.
I
+

OH

CaCO3, THF

B
OH

I
OH

B
OH

Pd(PPh3)4

Pd(PPh3)4
CaCO3, THF

10.8 Oxidation and Reduction in

Organic Chemistry

In organic chemistry, we say that oxidation occurs when

a carbon or hydrogen that is connected to a carbon atom
in a structure is replaced by oxygen, nitrogen, or halogen
Not defined as loss of electrons by an atom as in
inorganic chemistry
Oxidation is a reaction that results in loss of electron
density at carbon (as more electronegative atoms
replace hydrogen or carbon)
Oxidation: break CH (or (CC) and form CO, CN,
CX

Reduction Reactions

Organic reduction is the opposite of oxidation

Results in gain of electron density at carbon (replacement of
electronegative atoms by hydrogen or carbon)

Reduction: form CH (or CC) and break CO, CN, CX