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Alkanes: Nomenclature,
Conformational Analysis, and an
Introduction to Synthesis
Propane
CH3CH2CH3 or
Butane
CH3CH2CH2CH3 or
Pentane
CH3CH2CH2CH2CH3 or
Chapter 4 2
gBranched alkanes have at least one carbon which is attached to
more than two other carbons
Isobutane
CH3 CH CH3
CH3
Isopentane
Neopentane
CH3
CH3 C CH3
CH3
Chapter 4 3
gConstitutional isomers have different physical properties (melting
point, boiling point, densities etc.)
H Constitutional isomers have the same molecular formula but differentconnectivity
of atoms
C6H14 CH3CH2CHCH2CH3 20
-118 63.3 0.6643 1.3765
CH3
CH3
CH3
a
Unless otherwise indicated, all boiling points given in this book are at 1 atm or 760 torr.
b
The superscript indicates the temperature at which the density was measured
c
The index of refraction is a measure of the ability of the alkane to bend (refract) light rays. The values reported are
for light of teh D line of the sodium spectrum ( nD )
Chapter 4 4
gThe number of constitutional isomers possible for a given
molecular formula increases rapidly with the number of carbons
Possible Number of
Molecular Formula Constitutional Isomers
C4H10 2
C5H12 3
C6H14 5
C7H16 9
C8H18 18
C9H20 35
C10H22 75
C15H32 4,347
C20H42 366,319
C30H62 4,111,846,763
C40H82 62,481,801,147,341
Chapter 4 5
t IUPAC Nomenclature of Alkanes, Alkyl Halides
and Alcohols
gBefore the end of the 19th century compounds were named using
nonsystematic nomenclature
gThese "common" or "trivial" names were often based on the
source of the compound or a physical property
gThe International Union of Pure and Applied Chemistry (IUPAC)
started devising a systematic approach to nomenclature in 1892
gThe fundamental principle in devising the system was that each
different compound should have a unique unambiguous name
gThe basis for all IUPAC nomenclature is the set of rules used for
naming alkanes
Chapter 4 6
l Nomenclature of Unbranched Alkanes
Number of Number of
Carbon Carbon
Atoms Structure Name Atoms Structure
5
CH3(CH2)3CH3 Heneicosane 21 CH3(CH2)19CH3
Chapter 4 7
l Nomenclature of Unbranched Alkyl groups
gThe unbranched alkyl groups are obtained by removing one
hydrogen from the alkane and named by replacing the -ane of the
corresponding alkane with -yl
CH3 CH2 Et
CH3CH2 H
becomes
Ethane Ethyl
Propane Propyl
Butane Butyl
Chapter 4 8
l Nomenclature of Branched-Chain Alkanes (IUPAC)
gLocate the longest continuous chain of carbons; this is the parent
chain and determines the parent name.
CH3CH2CH2CH2 CHCH3
CH2
CH3
6 5 4 3 2 1
7 6 5 4 3
CH3CH2CH2CH2 CHCH3
CH3CH2CH2CH2 CHCH3
2 CH
CH3 2
1 CH3
2- Methylhexane 3-Methylheptane
Chapter 4 9
gWhen two or more substituents are identical, use the prefixesdi-,
tri-, tetra- etc.
HCommas are used to separate numbers from each other
HThe prefixes are used in alphabetical prioritization
gWhen two chains of equal length compete to be parent, choose
the chain with the greatest number of substituents
7 6 5 4 1
3 2
H3C CH2 CH CH CH CH CH3
CH2
CH3
2,3,5-Trimethyl-4-propylheptane
(four substituents)
Chapter 4 10
l Nomenclature of Branched Alkyl Chains
gTwo alkyl groups can be derived from propane
Three-Carbon Groups
CH 3 CH 2CH 2
Propylgroup
CH3CH2CH3
Propane
CH3 CH
CH3
1- Methylethyl or isopropyl group
CH3
1-Methylpropil or sec-butyl group
CH3 CH CH2
CH3
H3C CHCH3 2-Methylpropil or isobutyl group
CH3
CH3
CH3C
Isobutane CH3
1,1-Dimethylethyl or tert-butyl group
Chapter 4 11
gThe neopentyl group is a common branched alkyl group
CH3
H 3C C CH2
CH3
2,2-Dimethylpropyl or neopentyl group
gExamples
CH3CH2 CH2 CH CH2CH2 CH3
CH3 CH
CH3
4-(1-Methylethyl)heptane or 4-isopropylheptane
CH3 C CH3
CH3
4-(1,1-Dimethyethyl)octane or 4-tert-butyloctane
Chapter 4 12
t Classification of Hydrogen Atoms
gHydrogens take their classification from the carbon they are
attached to
1o Hydrogens atoms
CH3
Chapter 4 13
l Nomenclature of Alkyl Halides
gIn IUPAC nomenclature halides are named as substituents on the
parent chain
CH3 CH3
2-Chloro-3-methylpentane 2-Chloro-4-methylpentane
Chapter 4 14
l IUPAC Substitutive Nomenclature
gAn IUPAC name may have up to 4 features: locants, prefixes,
parent compound and suffixes
gNumbering generally starts from the end of the chain which is
closest to the group named in the suffix
CH3
4-Methly-1-hexanol
Chapter 4 15
gExamples
CH3
3 2 1 1 2 3 4 5
Cl CH 2 CH2 CH 2 OH H 3C CH CH2 C CH3
OH CH3
3-Chloro-1-propanol 4,4-Dimenthyl-2-pentanol
or 3-Chloropropan-1-ol or 4,4-dimenthyipentana-2-ol
gCommon Names of simple alcohols are still often used and are
approved by IUPAC
H3C CH2CH2OH H3C CH2 CH2 CH2OH H3C CH2 CH CH3
OH
Propyl alcohol Butyl alcohol
CH3 CH3
Chapter 4 16
gAlcohols with two hydroxyls are called diols in IUPAC nomenclature and glycols in
common nomenclature
Chapter 4 17
t Nomenclature of Cycloalkanes
lThe prefix cyclo- is added to the name of the alkane with
the same number of carbons
gWhen one substituent is present it is assumed to be at position
one and is not numbered
gWhen two alkyl substituents are present the one with alphabetical
priority is given position 1
gNumbering continues to give the other substituent the lowest
number
gHydroxyl has higher priority than alkyl and is given position 1
gIf a long chain is attached to a ring with fewer carbons, the
cycloalkane is considered the substituent
Chapter 4 18
CH3
CH 2CH 3
CH 3CHCH 3 CH3 1
2
3
4
CH2CH3 Cl
Isopropylcyclohexane 1-Ethyl-3-methylcyclohexane 4-Chloro-2-ethyl-1-methylcyclohexane
(not 1-ethyl-5-methylcyclohexane) (not 1-chloro-3-ethyl-4-methylcyclohexane
CH3
Cl
CH3
Chlorocyclopentane 2-Methylcyclohexanol
1-Cyclobuthylpentane
1,3-Dicyclohexylpropane
Chapter 4 19
t Bicyclic compounds
gBicyloalkanes contain 2 fused or bridged rings
gThe alkane with the same number of total carbons is used as the
parent and the prefix bicyclo- is used
One-carbon
Bridgehead
bridge
CH
CH2 CH2
Two-carbon Two-carbon
CH2
bridge bridge =
CH2 CH2
CH
Bridgehead
A bicycloheptane
7 1 3
8
CH3 3 H3C 8
6 4
6 7
5 4 5
8-Methylbicyclo[3.2.1]octane 8-Methylbicyclo[4.3.0]nonane
Chapter 4 20