10.

Organohalides

Based on McMurry’s Organic Chemistry, 7th edition

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Organohalides

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Why this Chapter?
 We'll begin in this chapter with a look at how
to name and prepare alkyl halides, and we'll
see several of their reactions.

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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)

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 If different halogens are present, number all and list
them in alphabetical order when writing the name.

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Naming if Two Halides or Alkyl Are
Equally Distant from Ends of Chain
 Begin at the end nearer the substituent whose name
comes first in the alphabet

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 Many simple alkyl halides are also named by
identifying first the alkyl group and then the halogen .

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10.2 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 on carbon
and slight negative on halogen

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10.3 Preparing Alkyl Halides from
Alkanes: Radical Halogenation
 The reaction of an alkane with Cl2 or Br2 through
aradical chain-reaction pathway.

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10.3 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

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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)

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Relative Reactivity
 Based on quantitative analysis of reaction products,
relative reactivity is expected
 Order parallels stability of radicals
 Reaction difference is more selective with bromine
than chlorine

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10.4 Preparing Alkyl Halides from
Alkenes: Allylic Bromination
 There are several methods for preparing alkyl halides from
alkenes, including the reaction of HX and X2 with alkene in
electrophilic addition reactions.
 N-bromosuccinimide (NBS) selectively brominates allylic
positions
 Requires light for activation
 A source of dilute bromine atoms

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Allylic Stabilization
 Allyl radical is electron delocalized
 More stable than typical alkyl radical by 45 kJ/mol (9
kcal/mol
 Allylic radical is more stable than tertiary alkyl radical

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Use of Allylic Bromination
 Allylic bromination with NBS creates an allylic
bromide
 Reaction of an allylic bromide with base produces a
conjugated diene, useful in synthesis of complex
molecules

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10.5 Stability of the Allyl Radical:
Resonance Revisited
 Three electrons are delocalized over three carbons
 Spin density surface shows single electron is
dispersed

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Allylic bromintation of an unsymmetrical alkene often leads
to a mixture of products.

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What products would you expect from reaction of 4,4-
dimethylcyclohexene with NBS?

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 The major product of the reaction of
methylenecyclohexane with N-bromosuccinimide is
1-(bromethyl)cyclohexene. Explain.

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10.6 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 tertiary
alcohol
 Primary and secondary alcohols react very slowly
and often rearrange, so alternative methods are used

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 The reaction of HX(HCl or HBr) with a tertiary alcohol

 Primary and secondary alcohols are best converted

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 How would you prepare the following alkyl
halides from the corresponding alcohols?

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10.7 Reactions of Alkyl Halides:
Grignard Reagents
 Reaction of RX with Mg in ether or THF
 Product is RMgX – an organometallic compound (alkyl-metal
bond)(alkylmagnesium halides) called Grignard regents
 R is alkyl 1°, 2°, 3°, aryl, alkenyl
 X = Cl, Br, I

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10.8 Organometallic combination
Reactions
 Alkyllithium (RLi) forms from RBr and Li metal
 RLi reacts with copper iodide to give lithium dialkylcopper
(Gilman reagents)
 Lithium dialkylcopper reagents react with alkyl halides to give
alkanes.the reaction is useful in Organic synthesis ,preparation
of larger molecules from smaller ones.

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The value of Organometallic
Coupling in Synthesis
 Coupling of two organometallic molecules produces
larger molecules of defined structure
 Aryl and vinyl organometallics also effective
 Coupling of lithium dialkylcopper molecules proceeds
through trialkylcopper intermediate

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10.9 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
 Oxidation is a reaction that results in loss of electron
density at carbon (as more electronegative atoms
replace hydrogen or carbon)

Oxidation: break C-H (or C-C) and form C-O,

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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 C-H (or C-C) and break C-O, C-N, C-X

second reaction at top of p. 349 here

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Oxidation Levels
 Functional groups are associated with specific levels
 Any reaction that converts a compound from alower
level to a higher level is an oxidation.
 Any reaction that converts a compound from higher
level to a lower level is a reduction
 Any reaction that doesn't change the level is nether
an oxidation nor areduction.

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 Comparing oxidation levels of compounds
Rank the following compounds in order of
increasing oxidation level:

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 Tell whether each of the following reaction is
an oxidation, a reduction, or neither.

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