ORGANIC CHEMISTRY

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Chapter 4: ALKANES

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NOMENCLATURE OF ALKANES

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ALKYL SUBSTITUENTS

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IUPAC NAMES OF BRANCHED
ALKANES

Determine the parent hydrocarbon – the

longest continuous carbon chain 5
•Substituents are listed
in alphabetical order
•Carbon chain is
numbered with the
lowest possible number
in the compound

Substituents are
the same 6
•Di, tri, tetra, n, sec, and tert are ignored in alphabetizing
substituents
• Iso, neo, and cyclo are not ignored

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NATURAL SOURCES OF ALKANES
C1-4

C5-11

Natural gas &

C9-16
petroleum
(fossil fuels) C15-25

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 PREPARATION OF ALKANES

Catalytic
hydrogenations
of alkenes /
alkynes

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Reduction reactions

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 Wurtz reactions symmetric alkane

Limitations:
+ The Wurtz reaction is limited to the synthesis of symmetric
alkanes from alkyl iodides & bromides
+ If two dissimilar alkyl halides are taken as reactants, then
the product is a mixture of alkanes that is, often, difficult to
separate
+ A side reaction also occurs to produce an alkene
+ The side reaction becomes more significant when the alkyl
halides are bulky at the halogen-attached carbon 12
Corey-House synthesis – the reaction of a lithium dialkyl
cuprate with an alkyl halide to form a new alkane

Corey-House synthesis overcomes some of

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the limitations of the Wurtz reaction
Exercise
Prepare following compounds from 1-bromo-3-
methylbutane, organic solvents, organic chemicals
containing 2 carbons and inorganic chemicals:
 REACTIVITY OF ALKANES
• Alkanes have only strong  bonds
•Electronegativity of C & H are approximately
the same
•None of the atoms in alkanes have any
significant charge
•Neither nucleophiles nor electrophiles are
attracted

Alkanes are very unreactive

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HALOGENATION OF ALKANES

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 PRODUCT DISTRIBUTION

It must be easier to abstract a hydrogen atom from a

secondary carbon than from a primary carbon 18
Reactivity - relative rate at which a particular hydrogen is
abstracted in chlorination reactions:

At room
temperature

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Product distribution can be estimated:

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Br2 is less reactive towards alkane than Cl2, but Br2 is
more selective

Bromination at 125 oC

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Too violent

Too slow

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Exercise
Products? & product distribution?
 Products? & product distribution?

% (A) = (12 x 1) / (12 x 1 + 2 x 1600 + 4 x 82) = 0.3%

% (B) = (2 x 1600) / (12 x 1 + 1600 x 2 + 4 x 82) = 90.4%
% (C) = (4 x 82) / (12 x 1 + 1600 x 2 + 4 x 82) = 9.3%
Exercise
Compare reactivity of following cases in the
monobromination with Br2 at 125 oC:
Compare reactivity of following cases in the
monobromination with Br2 at 125 oC:
Exercise
Which constitutional isomers of hexane can give
3 monosubstituted products when reacting with Cl2
at high temperature or under UV light:
 Which constitutional isomers of hexane can give
3 monosubstituted products when reacting with Cl2
at high temperature or under UV light:
 STEREOCHEMISTRY OF RADICAL
SUBSTITUTION REACTIONS

Have no
asymetric
carbon

Racemic
mixture
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Already have
1 asymetric
carbon

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Exercise
Draw all isomers (also including stereoisomers)
that can be formed in the monochlorination of
(S)-2-chloropentane:
Draw all isomers (also including stereoisomers)
that can be formed in the monochlorination of
(S)-2-chloropentane:
Exercise
Which following isomers are not the products
of the monobromination of (S)-2-bromopentane
to form 2,3-dibromopentane?
 Which following isomers are not the products
of the monobromination of (S)-2-bromopentane
to form 2,3-dibromopentane?
COMBUSTION OF ALKANES

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Exercise What is (A)?
Exercise
From cyclohexane, NBS, peroxide, organic
solvents, and inorganic chemicals, prepare: