John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 10
Organohalides

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Learning Objectives
(10.1)
 Names and structures of alkyl halides
(10.2)
 Preparing alkylhalides from alkanes: Radical
halogenation
(10.3)
 Preparing alkyl halides from alkenes: Allylic
bromination
(10.4)
 Stability of the allyl radical: Resonance revisited

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Learning Objectives
(10.5)
 Preparing alkyl halides from alcohols
(10.6)
 Reactions of alkyl halides: Grignard reagents
(10.7)
 Organometallic coupling reactions
(10.8)
 Oxidation and reduction in organic chemistry

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Organohalides and Alkyl
Halides
 Organohalide is an organic compound containing at
least one or more halogen atoms
 Found in abundance in nature
 Used as a solvent, inhaled anesthetic, and fumigant
 Alkyl halides comprise a halogen atom bonded to a
saturated, sp3-hybridized carbon atom

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1. Names and Structures of
Alkyl Halides
 Alkanes with a halogen substitute are termed as
haloalkanes
 Halogen is considered as a substituent on the
parent alkane chain

 Naming alkyl halides:

 Step 1 - Longest chain is named the parent
 Contains double or triple bond if present

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Names and Structures of Alkyl
Halides
 Step 2 - Carbons of the parent chain are
numbered beginning at the end closer to the first
substituent (lowest possible numbers)

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Names and Structures of Alkyl
Halides
 When more than one halogen is present, each are
numbered and listed in alphabetical order when
writing the name

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Names and Structures of Alkyl
Halides
 Step 3 - If the parent chain can be properly
numbered from either end by step 2, numbering
begins at the end closer to the substituent that
has alphabetical precedence

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Names and Structures of Alkyl
Halides
 Apart from the systematic naming convention,
identification of the first alkyl group and then the
halogen provides the names of many alkyl
halides
 CH3I is called iodomethane or methyl iodide

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Comparison of the
Halomethanes
 With progression down the periodic table:
 Size of halogens increase
 C–X bond lengths increase
 C–X bond strengths decrease

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Polarity of C─X Bonds
 Halomethanes possess a substantial dipole
moment
 Slight positive charge (δ+) on carbon atoms
 Slight negative charge (δ-) on halogens
 C─X carbon atom is considered to behave as an
electrophile in polar reactions

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2. Preparing Alkyl Halides from
Alkenes: Radical Halogenation
 Alkanes react
with Cl2 or Br2 in
the presence of
light through a
radical chain-
reaction pathway,
producing simple
alkyl halides

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Preparing Alkyl Halides from
Alkanes: Radical Halogenation
 Requirements of a radical substitution reaction
 Initiation, propagation, and termination
 Preparation of alkyl halides by alkane
halogenation results in mixtures of compounds

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Radical Halogenation of
Alkanes

(70/4 : 30/6 = 17.5 : 5 = 3.5 : 1)

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Radical Halogenation of
Alkanes
 Complications are more in cases of alkanes that
have more than one kind of hydrogen

 A reactivity order can be calculated toward

chlorination for different kinds of hydrogen
atoms (35/1 : 65/9 ≈ 35:7 = 5:1)
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Radical Halogenation of
Alkanes
 Based on quantitative analysis of reaction
products, relative reactivity is estimated
 With reference to energy required to break C–H
bonds, resultant tertiary radicals are more stable
than primary or secondary radicals

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Worked Example
 Draw and name all monochloro products that
can be obtained from radical chlorination of 2-
methylpentane
 Identify chiral products if present

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Worked Example
 Solution:

 Products at sites a, c, and e are chiral

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3. Preparing Alkyl Halides from
Alkenes: Allylic Bromination
 Alkenes react with N-bromosuccinimide (NBS)
in the presence of light to produce alkyl halides
 Hydrogen is substituted by bromine at the allylic
position

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Figure 10.2 - Mechanism of Allylic
Bromination of an Alkene with NBS

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Electrophillic Addition of HX &
X2 to Alkenes (7-7, 8-2)

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Relation Between Bromination and
Bond Dissociation Energies
 Bond dissociation energies help determine the
relative stabilities of various kinds of radicals

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4.Stability of the Allyl Radical:
Resonance Revisited
 Radical carbon atom adopts sp2-hybridization
 Structure is electronically symmetrical
 p orbital on the central carbon overlaps equally
with p orbitals on neighboring carbons

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Stability of the Allyl Radical:
Resonance Revisited
 Electronic symmetry of the allyl radical is the reason it
possesses two resonance forms
 High number of resonance forms result in increased
stability of the compound
 Bonding electrons are attracted to more nuclei
 According to molecular orbital terms, stability of an allyl
radical is because the unpaired electron is delocalized
rather than localized at one site
 Delocalization causes allyl radicals to react with Br2,
producing a mixture of products

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Stability of the Allyl Radical:
Resonance Revisited

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Stability of the Allyl Radical:
Resonance Revisited
 Allylic bromination products are converted into
dienes by dehydrohalogenation with a base

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Stability of the Allyl Radical:
Resonance Revisited

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Worked Example
 Mention the products formed when the following
alkene reacts with NBS
 Show the structures of all products formed

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Worked Example
 Solution:

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5. Preparing Alkyl Halides from
Alcohols
 Treating alcohol with HCl, HBr, or HI is the
simplest method of deriving alkyl halides
 Rate of reaction in primary and secondary
alcohols is slower and occurs at higher
temperatures

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5. Preparing Alkyl Halides from
Alcohols
 Rate of reaction in tertiary alcohols is faster and
occurs at low temperatures

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Preparing Alkyl Halides from
Alcohols
 Optimal conversion of primary or secondary
alcohols into halides is possible by treatment
with thionyl chloride or phosphorus tribromide

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6. Reactions of Alkyl Halides:
Grignard Reagents
 Reaction of RX with Mg in ether or THF,
produces Grignard reagents (RMgX)

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Reactions of Alkyl Halides:
Grignard Reagents
 Carbon atom of Grignard reagents is both basic
and nucleophilic

 Grignard reagents are formally magnesium

salts, R3C-+MgX, of a carbon acid, R3C–H
 It is a carbanion

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Worked Example
 Mention how a halogen substituent can be
replaced by a deuterium atom in the preparation
of a deuterated compound

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Worked Example
 Solution:
 In the reaction with deuterium donors, Grignard
reagents convert R–MgX into RD
 Similar to Grignard reacting with proton donors to
convert R–MgX into R–H

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7. Organometallic Coupling
Reactions
 Preparation of organometallic compounds is similar to
that of Grignard reagents
 Lithium metal reacts with alkyl halide to form
alkyllithium reagents

 Lithium diorganocopper compounds are called Gilman

reagents

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Organometallic Coupling
Reactions
 Gilman reagents undergo coupling reactions with
organochlorides, bromides, and iodides

 Coupling reactions from carbon–carbon compounds

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Organometallic Coupling
Reactions

Organometallic Compounds

R-Mg : high reactivity, strong nucleophile

R2CuLi : weak reactivity, Only 1 R is reactive

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The Suzuki–Miyaura Reaction
(suzuki coupling reaction)
 Coupling reaction of an aromatic or vinyl substituted
boronic acid with an aromatic or vinyl substituted
organohalide in the presence of a base and a palladium
catalyst

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Figure 10.5 - Mechanism of the Suzuki–
Miyaura Coupling Reaction

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Worked Example
 Carry out the following transformation using an
organo-copper coupling reaction

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Worked Example
 Solution:
 Octane is the product of an organometallic
coupling reaction between 1-bromobutane and
lithium dibutylcopper
 1-bromobutane yields the Gilman reagent

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10. Oxidation and Reduction in
Organic Chemistry
 Oxidation decreases electron density on carbon
 Forms C–O, C–N, C–X, or breaks C–H

 Reduction increases electron density on carbon

 Forms C–H (or C–C) or breaks C–O, C–N, C–X

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Oxidation & Reduction
Reactions
 Chlorination reaction of methane is an oxidation
 C–Cl bond is broken and a C–H bond is formed

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Figure 10.6 - Oxidation Levels
of Common Compounds
 Alkanes have the highest number of C–H bonds
per carbon
 CO2 Has the highest number of C–O bonds per
carbon

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Worked Example
 Classify the following reaction as an oxidation,
reduction, or neither

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Worked Example
 Solution:
 It is neither an oxidation nor a reduction
 In the double bond:
 The oxidation level of the upper carbon changes
from 0 to +1 in the product
 The oxidation level of the lower carbon changes
from 0 to -1
 Both the product and the reactant have the same
total oxidation level

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Summary
 Alkyl halides undergo reactions that are well-
studied and are considered very important in the
field of organic chemistry
 Alkyl halides can be prepared by the reaction of
alkenes and N-bromosuccinimide (NBS)
 Grignard reagents (RMgX) are formed when
alkyl halides react with magnesium in an ether
solution
 Gilman reagents are formed when alkyl halides
react with lithium metal in the presence of
copper iodide
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Problems
 14,15, 18, 22, 26, 31, 33, 34, 36, 46

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